| Autor: |
Nathan Coutard, Charles B. Musgrave, Jisue Moon, Nichole S. Liebov, Robert M. Nielsen, Jonathan M. Goldberg, Meijun Li, Xiaofan Jia, Sungsik Lee, Diane A. Dickie, William L. Schinski, Zili Wu, John T. Groves, William A. Goddard, T. Brent Gunnoe |
| Rok vydání: |
2022 |
| Předmět: |
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| Zdroj: |
ACS Catalysis. 12:5356-5370 |
| ISSN: |
2155-5435 |
| DOI: |
10.1021/acscatal.2c00982 |
| Popis: |
The catalytic partial oxidation of methane is achieved at low temperatures (90% at ∼35% methane conversion at approximately 6 turnovers. Under our catalytic methane oxidation reaction conditions, MeTFA is stable against overoxidation, which explains the likely high selectivity at conversions >15%. Using combined experimental studies and DFT calculations, a mechanism involving soluble and molecular Mn species in the catalytic cycle is proposed. The proposed reaction pathway involves initial activation of Mnᴵᴵ by dioxygen, cleavage of a methane C–H bond by a Mnᴵᴵᴵ hydroxo intermediate, rebound of the methyl radical to generate MeTFA, and finally regeneration of the starting MnII complex. Also, this process is shown to be applicable to the oxidation of ethane, favoring the mono-oxidized product ethyl trifluoroacetate (EtTFA) and reaching ∼46% conversion. |
| Databáze: |
OpenAIRE |
| Externí odkaz: |
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